Electrolyte electroreflectance (EER) experiments were performed onIn0.22Ga0.78As/GaAssingle quantum wells grown by the conventional molecular-beam-epitaxy (MBE) shutter operation, and also by modified MBE shutter operation intended to form more compositionally abrupt normal and inverted interfaces. The latter included controlled thermal desorption of the surface segregated In at the InGaAs layer surface (flash off), and the deposition of In at the InGaAs/GaAs interface to eliminate compositional broadening (predeposition). The fundamental energy gap and subband transitions were determined experimentally, and compared with an accurate calculation of the potential well problem including strain. These results confirmed the segregation of In atoms near the interface. The segregation was maximum in the conventional (normal) MBE sample and least with the modified growth incorporating predeposition and flash off, as expected. The segregated atoms are observed to act as dopants and form junctions near the InGaAs/GaAs interface. This study shows that EER can be used as an effective tool for studying the segregation process in MBE growth. ©1997 American Institute of Physics.